CN101231357B - Laminated diffraction optical element - Google Patents
Laminated diffraction optical element Download PDFInfo
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- CN101231357B CN101231357B CN200810005146XA CN200810005146A CN101231357B CN 101231357 B CN101231357 B CN 101231357B CN 200810005146X A CN200810005146X A CN 200810005146XA CN 200810005146 A CN200810005146 A CN 200810005146A CN 101231357 B CN101231357 B CN 101231357B
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Abstract
A multi-layered diffraction optical element, comprises a transparent substrate, a first layer having a diffraction grating shape at least on one face and comprised of a relatively high refractive index and low dispersion material, and a second layer having a diffraction grating shape at least on one face and comprised of a relatively low refractive index and high dispersion material, wherein the first and second layers are laminated on the transparent substrate so that the respective diffraction grating shapes are mutually opposed to each other with no space therebetween, and, the first layer is comprised of a first organic resin including a first inorganic fine particle, and the second layer is comprised of a second organic resin including a second inorganic fine particle different from the first inorganic fine particle.
Description
Technical field
The present invention relates to comprise not have the stacked high chromatic dispersion material of low-refraction of mode at interval and the multilayer diffraction optical element of high-refractivity and low-dispersion material therebetween.
Background technology
Up to now, utilize the diffraction optical system of diffraction of light generally to have the compound lens that comprises the different glass material of dispersion characteristics, reduce aberration thus.For example, in such as telescopical object lens, the little glass material of chromatic dispersion is used as positive lens, and the glass material that chromatic dispersion is big is used as negative lens, and by being used in combination of these lens, the aberration that appears on the optical axis obtains proofreading and correct.But, when the configuration of lens and quantity are limited, maybe when the glass material that will be used is limited, usually find to be difficult to correcting chromatic aberration fully.
Non-patent document 1 (A.D.Kathman and S.K.Pitalo, " Binary Optics inLens Design ", International Lens Design Conference, 1990, SPIE Vol.1354, p297～309) being used in combination of diffraction optical element that discloses the diffraction optical element with diffraction surfaces and had a diffraction grating can be reduced aberration with the lens of the use of lesser amt.
This has utilized as the plane of refraction of optical parameter and diffraction surfaces and has produced the opposite physical phenomenon of direction for the light of reference wavelength at aberration.By changing the cycle of the diffraction grating that in refraction optical element, forms continuously, can produce characteristic with the non-spherical lens equivalence.
But a branch of light that enters diffraction optical element is divided into the multi-beam of each order by diffraction.At this moment, the diffraction light beyond the design order becomes the generation reason of solar flare (flare) thus in the light position imaging in addition of design order.
United States Patent (USP) 5847877 discloses the dispersion of refractive index of each optical element and realized higher diffraction efficiency on the optimised wavelength coverage that makes at broad of the configuration of the grating that forms on the border surface of optical element.The luminous flux of wavelength available scope is focused on the specific order (hereinafter referred to as the design order), suppresses the diffraction light intensity of other diffraction order thus and prevents solar flare.
United States Patent (USP) 5847877 discloses in order to obtain to have the configuration of higher diffraction efficiency on the wavelength coverage of broad, the use that is combined of the diffraction optical element that is formed by the material with relatively low dispersion of refractive index and the diffraction optical element that is formed by the material with relative higher dispersion of refractive index.
That is, the difference between the dispersion of refractive index of height and low-refraction chromatic dispersion material is high more, and then the thickness of the diffraction grating of the optical element that will form is more little, makes the field angle of optical element broaden.Therefore, for higher accuracy correction aberration, must use material with very high dispersion of refractive index (Abbe number is little) and material with low-down dispersion of refractive index (Abbe number is big).
The pass that United States Patent (USP) 7031078 discloses between refractive index (nd) and the Abbe number (vd) is nd＞-6.667 * 10
-3The secondary dispersion of vd+1.07 and refractive index (θ g, F) and the pass between the Abbe number (vd) be θ g, F≤-2vd * 10
-3+ 0.59 optical material.By satisfying these formula, the refraction efficient in the whole visibility region can be enhanced.
Optical material in the U.S. Patent No. 6059411 is to mix as fine particle in adhesive resin and disperse dispersion of refractive index higher and show the compound substance of the transparent conductive metal oxide of the lower person's character of secondary dispersion characteristic.As the transparent conductive metal oxide, such as ITO, ATO, SnO
2, ZnO the transparent conductive metal oxide be disclosed.
The embodiment of U.S. Patent No. 7031078 also discloses so that the stacked diffraction optical element that spaced mode is oppositely arranged the diffraction optical element that comprises the material with high refraction and high chromatic dispersion and comprises the diffraction optical element of the material with low refraction and low chromatic dispersion to be set betwixt.
On the other hand, the needs for the product miniaturization greatly increase in the optical device that uses optical element.Therefore, be used to make the thin as much as possible exploitation of the thickness of optical element in process.Thus, developed be not above-mentioned at ground floor diffraction optical element and the diffraction optical element of the second layer between have stacked diffraction optical element at interval, but do not have the multilayer diffraction optical element of type at interval.U.S. Patent No. 6759471 discloses the multilayer diffraction optical element that does not have type at interval.
But, in United States Patent (USP) 3759471, in the optical element of explanation, wherein be dispersed with the high chromatic dispersion material of low-refraction of fine inorganic particle and the combination of high refractive low dispersive glass and be used.Normally, the linear expansion coefficient of organic resin is than big 1 or 2 order of magnitude of glass (digit).
And the above-mentioned difference between the linear expansion coefficient is relevant greatly to dependence on temperature with refractive index, makes refractive index difference between organic resin and the glass change greatly according to temperature variation and reduces diffraction efficiency.
Summary of the invention
The objective of the invention is, a kind of multilayer diffraction optical element is provided, the distortion that is caused by interfacial stress of this multilayer diffraction optical element is suppressed, and owing to has the reduction of the diffraction efficiency that the change of the diffraction efficiency in the multilayer diffraction optical element of high-diffraction efficiency causes and be suppressed.
The invention provides a kind of multilayer diffraction optical element, in this multilayer diffraction optical element, on the face of transparency carrier, at least have the diffraction grating shape and comprise the ground floor of relative high-refractivity and low-dispersion material and the second layer that has the diffraction grating shape and comprise the high chromatic dispersion material of relative low-refraction in a side at least by there not to be stacked setting of mode at interval therebetween in a side, and, ground floor comprises the organic resin that contains first fine inorganic particle, and the second layer comprises the organic resin that contains second fine inorganic particle different with first fine inorganic particle.
The invention provides a kind of multilayer diffraction optical element, in this multilayer diffraction optical element, having the high refractive index that reflects the d line of the material that hangs down chromatic dispersion is taken as more than or equal to 1.54 and smaller or equal to 1.63, and Abbe number is taken as more than or equal to 44 and smaller or equal to 57, the refractive index of d line with material of low refraction high-dispersion is taken as more than or equal to 1.48 and smaller or equal to 1.57, and Abbe number is taken as more than or equal to 14 and smaller or equal to 28, and the refractive index difference that has the material of the low chromatic dispersion of high refraction and have a d line between the material of low refraction high-dispersion is taken as more than or equal to 0.024 and smaller or equal to 0.075.
The present invention is directed to a kind of multilayer diffraction optical element, this multilayer diffraction optical element comprises: transparency carrier; At least on a face, have the diffraction grating shape and comprise the ground floor of relative high-refractivity and low-dispersion material; At least on a face, have the diffraction grating shape and comprise the second layer of the high chromatic dispersion material of relative low-refraction, wherein, the ground floor and the second layer are laminated on the transparency carrier, make each diffraction grating shape not have mode at interval therebetween mutually toward each other, and, ground floor comprises first organic resin that contains first fine inorganic particle, and the second layer comprises second organic resin that contains second fine inorganic particle different with first fine inorganic particle.
The refractive index of the d line of high-refractivity and low-dispersion material can be for more than or equal to 1.54 and smaller or equal to 1.63, and Abbe number is more than or equal to 44 and smaller or equal to 57, and, the refractive index of the d line of the high chromatic dispersion material of low-refraction is more than or equal to 1.48 and smaller or equal to 1.57, and Abbe number is more than or equal to 14 and smaller or equal to 28, and the refractive index difference of the d line between the high chromatic dispersion material of high-refractivity and low-dispersion material and low-refraction is more than or equal to 0.024 and smaller or equal to 0.075.
In multilayer diffraction optical element, the average particle size of first and second fine inorganic particle can be for more than or equal to 1nm and smaller or equal to 100nm.First fine inorganic particle can comprise at least a type that is selected from Al, Zr, Y, Ga, La and oxide thereof and compound, and has more than or equal to 1.70 and smaller or equal to the refractive index of its d line of 2.5 with more than or equal to 30 and smaller or equal to 90 Abbe number.Scheme as an alternative, in multilayer diffraction optical element, the volume content of first fine inorganic particle in the ground floor can be 1～29vol%.
Second fine inorganic particle can be the electrically conducting transparent material.The electrically conducting transparent material can be ITO.
The organic resin that comprises in first and second layers can comprise at least a type that is selected from acryl resin, vinyl and epoxy resin.The organic resin that comprises in first and second layers can comprise ultraviolet curing (curing) resin.
With reference to the following explanation of accompanying drawing reading exemplary embodiment, it is fairly obvious that further feature of the present invention will become.
Description of drawings
Figure 1A and Figure 1B are the synoptic diagram of diffraction optical element.
Fig. 2 A is the synoptic diagram of the admixture of the organic resin of the low dispersive layer of the high refraction of expression and inorganic resin.
Fig. 2 B is the synoptic diagram of the admixture of the organic resin of the low refraction high-dispersion layer of expression and inorganic resin.
Fig. 3 is the synoptic diagram of manufacture method that expression is used for the sample of refractometry.
Fig. 4 is the synoptic diagram that expression is used for the manufacture method of the sample that transmission coefficient measures.
Fig. 5 is that the part of assessment mould is amplified the synoptic diagram in cross section.
Fig. 6 is the synoptic diagram of manufacture method that expression has the assessment sample of shape transferability.
Fig. 7 A and Fig. 7 B are the synoptic diagram of mould method for releasing that expression has the assessment sample of shape transferability.
Fig. 8 A and Fig. 8 B are the synoptic diagram of the manufacture method of the expression sample that is used to assess diffraction efficiency.
Fig. 9 is the diagrammatic sketch of measurement result of the diffraction efficiency of expression example 1.
Figure 10 is the diagrammatic sketch of measurement result of the diffraction efficiency of expression example 2.
Figure 11 is the diagrammatic sketch of measurement result of the diffraction efficiency of expression example 3.
Figure 12 is the diagrammatic sketch of measurement result of the diffraction efficiency of expression example 4.
Figure 13 is the diagrammatic sketch of measurement result of the diffraction efficiency of expression example 5.
Figure 14 is the diagrammatic sketch of measurement result of the diffraction efficiency of expression comparative example 1.
Figure 15 is the diagrammatic sketch of measurement result of the diffraction efficiency of expression comparative example 2.
Figure 16 is the diagrammatic sketch of measurement result of the diffraction efficiency of expression comparative example 3.
Figure 17 is the diagrammatic sketch of measurement result of the diffraction efficiency of expression comparative example 4.
Figure 18 is the diagrammatic sketch of measurement result of the diffraction efficiency of expression example 6.
Figure 19 is the diagrammatic sketch of measurement result of the diffraction efficiency of expression example 7.
Figure 20 is the diagrammatic sketch of measurement result of the diffraction efficiency of expression example 8.
Figure 21 is the diagrammatic sketch of measurement result of the diffraction efficiency of expression example 9.
Figure 22 is the diagrammatic sketch of measurement result of the diffraction efficiency of expression example 10.
Figure 23 is the diagrammatic sketch of measurement result of the diffraction efficiency of expression example 11.
Embodiment
Exemplary embodiment of the present invention below is described.
(explanation of diffraction optical element)
To the representational whole configuration of diffraction optical element of the present invention be described by using Figure 1A and Figure 1B.
Figure 1A and Figure 1B are the synoptic diagram of multilayer diffraction optical element 100.Figure 1A is the end face view, and Figure 1B is the cross section.This diffraction optical element is configured to the low dispersive layer 2 of height refraction and low refraction high-dispersion layer 1 that have diffraction grating shape there not to be mode at interval to be laminated with therebetween comprising on the transparency carrier layer 3 of glass and plastics.Low refraction high-dispersion layer 1 can be opposite with the high stacked order that reflects low dispersive layer 2.Two faces of transparency carrier layer 3 all can be for smooth spherical or aspheric.
In order to improve the diffraction efficiency of optical element, the refractive index (n of the d line of low refraction high-dispersion layer 1
D1) must be than the refractive index (n of the d line of the low dispersive layer 2 of height refraction
D2) big, and the Abbe number (v of low refraction high-dispersion layer 1
D1) must be than the Abbe number (v of the low dispersive layer 2 of height refraction
D2) little.Here the Abbe number of mentioning is (the indication of the slope (inclination) of the refractive index among the 468.1nm～656.3nm) of expression visible region.Abbe number (v
d) calculate by following formula (1).
v
d=(n
d-1)/(n
f-n
c) formula (1)
n
d: d line (587.6nm) refractive index
n
f: f line (486.1nm) refractive index
n
c: c line (656.3nm) refractive index
The explanation of the low dispersive layer 2 of high refraction
The following describes the low dispersive layer of height refraction in the diffractive-optical element of the present invention.
Fig. 2 A is the cross section of the low dispersive layer 2 of the high refraction of expression, and wherein, the sub-5a of fine inorganic particle is dispersed among the organic resin 4a.Organic resin 4a preferably clear degree is higher, and the preferred material that uses one or more types that are selected from acryl resin, vinyl and epoxy resin.When material had the characteristic of hope, to the details of type of material without limits, and material can be the potpourri of independent or two or more type combination.
Refractive index (the n of organic resin 4a
2d) be preferably 1.50 or bigger, and Abbe number (v
2d) be preferably 40 or bigger.When refractive index and Abbe number are extremely low, even fine inorganic particle is supplied, do not realize the refractive index and the Abbe number of wishing yet, and can not be shown as the function of the low dispersive layer of height refraction.
When the low dispersive layer intention of height refraction is to be cured easily, wish that it is ultraviolet type.For example, can use and comprise ultraviolet curing acryl resin (RC-C001; Dainippon InkKagaku Kogyou, n
d=1.52, v
d=52), acrylic monomer (KAYARAD684; NIPPON KAYAKU CO., LTD.) and the resin (n of the potpourri of optional light trigger (optical initiator)
d=1.53, v
d=54).
The average-size of the sub-5a of fine inorganic particle is preferably more than and equals 1nm and smaller or equal to 100nm, and when average-size during less than 1nm, its viscosity (thickening) is enhanced when mixing with organic resin 4a, makes thus to be difficult to setting and to form.When average fine particle size during greater than 100nm, it is bigger that chromatic dispersion becomes, and the optical characteristics that can not obtain to wish.
Because the sub-5a of fine inorganic particle increases the refractive index of resin bed and make resin bed become low dispersive layer, so the refractive index n of d line
dBe preferably more than and equal 1.70 and smaller or equal to 2.5, and Abbe number v
dBe preferably more than and equal 30 and smaller or equal to 90.The sub-5a of fine inorganic particle is preferably selected from the oxide and the compound of Al, Zr, Y, Ga, La and these elements, and can be the potpourri of the element of two or more types.The nanometer fine particle of the oxide of Al, Zr and these elements also is devoted in the market for sale, and in view of the easiness and the manufacturing cost of available, these materials are preferred.
The shape of the sub-5a of fine inorganic particle can be sphere or uncertain, as long as and the characteristic that can obtain to wish, so for shape without limits, still, in view of the improvement of refractive index, this shape preferably has the minority pore.The face that also can give the sub-5a of fine inorganic particle is used to strengthen the coating of dispersibility, spreading agent is handled and face is handled.
Allow the sub-5a of fine inorganic particle to be dispersed in the refractive index (n of the d line of the low dispersive layer 2 of height refraction among the organic resin 4a
2d) be preferably more than and equal 1.54 and smaller or equal to 1.63.Abbe number (the v of the wavelength dispersion in the expression visibility region
2d) be preferably more than or equal to 44 and smaller or equal to 57 scope in.
The content ratio of the sub-5a of fine inorganic particle in the low dispersive layer 2 of height refraction is preferably more than and equals 1vol% and smaller or equal to 30vol%, more preferably more than or equal to 5vol% and smaller or equal to 26vol%.When this content ratio was exceedingly low than 5vol%, it is difficult that the refractive index of hope and the control of Abbe number become, and when it was exceedingly high than 26vol%, viscosity grow when adjusting made to be difficult to formalize and form thus.
When thickness was 30 μ m, the low dispersive layer 2 of high refraction was for being preferably 90% or bigger more than or equal to 400nm and smaller or equal to the average transmission coefficient of the wavelength of 700nm.Organic resin 4a can comprise the spreading agent that optional being used to improves the dispersibility of the sub-5a of fine inorganic particle.The content of spreading agent is being than preferably obtaining the dispersion effect of wishing and do not damaging in the scope of the needed characteristic of organic resin 4a, and particularly, this content ratio is preferably more than and equals 1.0 quality % and smaller or equal to 10 quality %.
(explanation of low refraction high-dispersion layer 1)
The following describes the low refraction high-dispersion layer 1 in the diffractive-optical element of the present invention.
Fig. 2 B is the schematic cross-section of the low refraction high-dispersion layer 1 of expression, and wherein, the sub-5b of fine inorganic particle is dispersed among the organic resin 4b.Organic resin 4b preferably clear degree is higher and refractive index is lower, and the preferred material that uses one or more types that are selected from acrylic based resin, fluorinated acrylamide acidic group resin, silicone and fluororesin.When material had the characteristic of hope, to the details of type of material without limits, and material can be the potpourri of independent or two or more type combination.
Refractive index (the n of organic resin 4b
1d) be preferably 1.53 or littler.When refractive index is high, even fine inorganic particle is supplied, does not realize the refractive index of wishing yet, and can not be shown as the function of low refraction high-dispersion layer.When low refraction high-dispersion layer intention is to be cured easily, wish that it is ultraviolet type.
Because the sub-5b of fine inorganic particle mixes with organic resin 4b to become low refraction high-dispersion, therefore, disperses preferably high as much as possible.As the example of the sub-5b of fine inorganic particle, can enumerate ITO, ATO, AZO, FZO, In
2O
3, ZnO, SnO
2, TiO
2, NB
2O
5, Cr
2O
3And BaTiO
3Especially, in view of diffraction efficiency, such as ITO, ATO, AZO, FZO, In
2O
3, ZnO and SnO
2The electrically conducting transparent material be preferred, and especially, in view of the secondary dispersion characteristic and the transparency, ITO is most preferred.
The average particle size of the sub-5b of fine inorganic particle is preferably more than and equals 1nm and smaller or equal to 100nm.When average particle size is minimum, to the influence of the face of fine particle even arrive fine particle inside, make the optical characteristics that loses fine inorganic particle.The increase of face treating agent brings the enhancing of viscosity when mixing with organic resin, makes thus to be difficult to setting and formation.When average particle size was very big, it is big that chromatic dispersion becomes, and the optical characteristics that can not obtain to wish.
Refractive index (the n of the d line of low refraction high-dispersion layer 1
1d) be preferably more than and equal 1.48 and smaller or equal to 1.57.Abbe number (the v of the wavelength dispersion in the expression visibility region
1d) preferably be in more than or equal to 14 and smaller or equal in 28 the scope.
The content ratio of the sub-5b of fine inorganic particle is preferably more than and equals 1vol% and smaller or equal to 30vol%, more preferably more than or equal to 5vol% and smaller or equal to 23vol%.When this content ratio was exceedingly low than 5vol%, it is difficult that the refractive index of hope and the control of Abbe number become, and when it was exceedingly high than 23vol%, viscosity grow when adjusting made to be difficult to formalize and form thus.
When under the situation about not having betwixt at interval on the low dispersive layer 2 of height refraction during stacked low refraction high-dispersion layer 1, the refractive index (n of the d line of low refraction high-dispersion layer 1
1d) and the high refractive index (n that reflects the d line of low dispersive layer 2
2d) between difference be preferably 0.024 or bigger.When it was lower than 0.024, because optical element wall etc., the solar flare coefficient increased.
(experimental example)
(adjustment of optical material and assessment)
Make high-refractivity and low-dispersion (dispersion) material and the high chromatic dispersion material of low-refraction that is used for low refraction high-dispersion layer 1 that are used for the low dispersive layer 2 of high refraction among the present invention at first, in the following manner.
The preparation of＜high-refractivity and low-dispersion material and assessment 〉
At first, in toluene solution, be dispersed with 10wt% zirconic slurry (average particle size: 3nm) with as the potpourri of the 1-hydroxy-cyclohexyl benzophenone of the two cyclopentene oxygen base ethyl-methyl propylene esters of the pentaerythritol triacrylate (pentaerythritoltriacrylate) of three (2-acrylyl oxy-ethyl) isocyanuric acid ester of the 25wt% of ultraviolet curing acryl resin, 30wt%, 43wt% and 2wt% (the refractive index n d=1.53 after the curing, vd=50) mixed.This mixed solution is placed in the evaporator, and pressure reduces from 10,000 handkerchiefs gradually at 45 ℃, up to final arrival 200 handkerchiefs.Toluene solution was dispersed in the atmosphere fully with 12 hours, made high-refractivity and low-dispersion materials A 1～A5 thus.Zirconic particle size is by the particle size distribution instrumentation amount of laser system (ELS:Otsuka Denshi manufacturing).
The volume fraction of fine inorganic particle of high-refractivity and low-dispersion materials A 1～A5 is A1 (23v%), A2 (20v%), A3 (18v%), A4 (10v%) and A5 (6v%).Though the volume fraction of fine inorganic particle is that the material Z1 of 30v% is also manufactured, it has produced higher viscosity among removing solution, so solution is not removed fully.
By replacing the type of fine inorganic particle, high-refractivity and low-dispersion materials A 6～A8 is made similarly.Fine inorganic particle uses aluminium oxide (average particle size: 20nm) be used for high-refractivity and low-dispersion materials A 6～A8, and the potpourri (the refractive index n d=1.53 after the curing, Abbe number vd=52) of the 1-hydroxy-cyclohexyl benzophenone of the tristane dimethanol diacrylate of use 98wt% and 2wt% is as the ultraviolet curing acryl resin.
The volume fraction of fine inorganic particle of high-refractivity and low-dispersion materials A 6～A8 is A6 (26v%), A7 (15v%) and A8 (7v%).In this case, similar with the zirconia dispersion resin, the volume fraction of fine inorganic particle is that the material Z2 of 30v% is also manufactured, but it has produced higher viscosity among removing solution, so solution is not removed fully.In the material of fine inorganic particle in high-refractivity and low-dispersion materials A 1～A8, organic fine particle and the mixing ratio of these materials shown in the table 1.
The preparation of the high chromatic dispersion material of low-refraction
At first, ((the refractive index n d=1.52 after the curing, Abbe number vd=51) is mixed for 15～20nm) slurry and ultraviolet curing acryl resin to be dispersed with the ITO fine particle of 10wt% in xylene solution.This mixed solution is placed in the evaporator, and pressure reduces from 5,000 handkerchiefs gradually at 45 ℃, up to final arrival 200 handkerchiefs.Xylene solution was dispersed in the atmosphere fully with 12 hours, prepared the high chromatic dispersion material L1～L9 of low-refraction thus.
The volume fraction of fine inorganic particle of the high chromatic dispersion material L1～L9 of low-refraction is L1 (16.0v%), L2 (14.1v%), L3 (12.9v%), L4 (7.9v%), L5 (5.4v%), L6 (7.6v%), L7 (4.8v%), L8 (2.9v%), L9 (8.7v%).In of the fine inorganic particle in the high chromatic dispersion material L1～L9 of low-refraction shown in the table 2 and the material of organic resin and the mixing ratio of these materials.
As above-mentioned ultraviolet curing acryl resin (the refractive index n d=1.52 after the curing, substituting Abbe number vd=51), ultraviolet curing acrylic based resin (the refractive index n d=1.43 after the curing, Abbe number vd=61) is used, and prepares the high chromatic dispersion material T1～T6 of low-refraction thus.
The volume fraction of fine inorganic particle of the high chromatic dispersion material T1～T6 of low-refraction is T1 (21.6v%), T2 (17.3v%), T3 (15.2v%), T4 (14.8v%), T5 (14.6v%) and T6 (13.0v%).In of the fine inorganic particle in the high chromatic dispersion material T1～T6 of low-refraction shown in the table 3 and the material of organic resin and the mixing ratio of these materials.
The assessment of optical characteristics
Carry out the assessment of the optical characteristics of the high chromatic dispersion material L1～L9 of high-refractivity and low-dispersion materials A 1～A8 and low-refraction then.Carry out the assessment of each optical characteristics in the following manner.
Refractive index
By as following, preparing the refractive index of each optical element of sample measurement.
At first, as shown in Figure 3, thickness is the distance piece 9 and high-refractivity and low-dispersion material 7 (A1～A8) be set on the high refracting glass 6 that thickness is 1mm of 50 μ m.On glass at this, thickness is that the quartz 8 of 1mm is mounted by distance piece 9, expands and launch to be made for the high-refractivity and low-dispersion material 7 of sample thus.This sample is at 20mW/cm
2With under 1000 seconds the condition by high pressure silver lamp (EXECURE 250, and by HOYA CANDEOOPTRONICS CO., LTD makes) irradiation, make sample solidifies thus.For the refractive index of g line 435.8nm, f line 486.1nm, e line 546.1nm, d line 587.6nm and c line 656.3nm, measure the sample that solidifies by using refractometer (KPR-30 is made by Shimadzu Corporation).Calculate Abbe number according to the refractive index of measuring.Refractive index and Abbe number at the materials A of high-refractivity and low-dispersion shown in the table 1 1～A8.As shown in table 1, the refractive index of high-refractivity and low-dispersion materials A 1～A8 is more than or equal to 1.54 and smaller or equal to 1.63, and Abbe number is more than or equal to 44 and smaller or equal to 57.
About the high chromatic dispersion material L1～L9 of low-refraction, be the distance piece of 12.5 μ m by used thickness, under identical condition, prepare sample, and measure refractive index by refractometer.Refractive index and Abbe number at the high chromatic dispersion material L1～L9 of low-refraction shown in the table 2.As shown in table 2, the refractive index of the high chromatic dispersion material L1～L9 of low-refraction is more than or equal to 1.53 and smaller or equal to 1.57, and Abbe number is more than or equal to 19 and smaller or equal to 39.
Transmissivity
By as following, preparing the transmissivity of each optical element of sample measurement.
At first, as shown in Figure 4, thickness is the distance piece 9 of 30 μ m and measures material 7 (high-refractivity and low-dispersion material (A1～A8) and the high chromatic dispersion material of low-refraction (L1～L9 and T1～T6)) is set on the glass substrate 8 that thickness is 1mm.On these materials and distance piece, thickness is that the glass substrate 8 of 1mm is mounted, and expands and launch to be made for the high-refractivity and low-dispersion material 7 of sample thus.This sample is at 20mW/cm
2With under 1000 seconds the condition by high pressure silver lamp (EXECURE 250, and by HOYA CANDEO OPTRONICSCO., LTD makes) irradiation, make sample solidifies thus.Interval with 10nm is measured the sample that solidifies to the transmissivity that reaches 400～800nm by spectrial photometer (U4000 is made by Hitachi Seisakusho), and calculates its mean value.
Transmissivity at the materials A of high-refractivity and low-dispersion shown in the table 1 1～A8.As shown in table 1, the transmissivity of high-refractivity and low-dispersion materials A 1～A8 is 96% or bigger, and it demonstrates and has good transmitance.Normally, when transmissivity is 90%, we can say good transmissivity is shown.About the high chromatic dispersion material L1～L9 of low-refraction and T1～T6, enough transmissivities are shown as optical element.
The assessment of shape transferability
By as following, preparing the shape transferability of each optical element of sample measurement.
Fig. 5 is that the part of assessment mould 12 is amplified the synoptic diagram in cross section.As shown in Figure 5, assessment mould 12 comprises the mould substrate layer 11 and the coating (plated layer) 10 with the raster shape on upper strata as basal layer.Being shaped as of coating 10, groove height d=14 μ m, spacing X=80 μ m, surface roughness Ra is 2nm or littler.
As shown in Figure 6, (high-refractivity and low-dispersion material (A1～A8) and the high chromatic dispersion material of low-refraction (L1～L9 and T1～T6)) is dropped on the assessment mould 12 to measure material 7, and on these materials, place sheet glass 13, thus their are stretched and launch to become gross thickness and be the resin of 30 μ m and be made for sample.This sample is at 20mW/cm
2With under 1000 seconds the condition by high pressure silver lamp (EXECURE 250, and by HOYA CANDEO OPTRONICSCO., LTD makes) irradiation, make sample solidifies (Fig. 7 A) thus.Shown in Fig. 7 B, discharge the sample that solidifies by mould release clip 14 from the resin that solidifies, it is parallel with surface level to make sheet glass 13 to remain, and observe its edge (edged) shape by non-contact tri-dimensional facial shape and roughness concentration instrument (New View 5000 is made by Zygo Corporation).
Observe the transfer shape of high-refractivity and low-dispersion materials A 1～A8 and Z1 and Z2, and in its result shown in the table 1.As shown in table 1, all edges of high-refractivity and low-dispersion materials A 1～A8 are transferred with good shape.In contrast, high-refractivity and low-dispersion material Z1 and Z2 can not obtain enough transferabilities.About the high chromatic dispersion material L1～L9 of low-refraction and T1～T6, also obtain good transferability.
The measurement of linear expansion coefficient
Measure the linear expansion coefficient of each optical element in the following manner.The part of substrate that is used for the sample of transmissivity measurement is removed and measures by TMA (by PerkinElmer, Inc. makes).Measurement result at the materials A of high-refractivity and low-dispersion shown in the table 1 1～A8.
Multilayer diffraction optical element 100
Then, with diffraction optical element that does not have the stacked use high-refractivity and low-dispersion of mode materials A 1～A8 at interval betwixt and the optical element that uses the high chromatic dispersion material L1～L9 of low-refraction and T1～T6, prepare multilayer diffraction optical element thus, and its assessment is performed.
Configuration at the multilayer diffraction optical element of example shown in the table 4 1～5 and comparative example 1～4.Example 1 is to use the diffraction optical element of high-refractivity and low-dispersion materials A 1 and the multilayer diffraction optical element of the diffraction optical element that uses the high chromatic dispersion material L1 of low-refraction.Similarly, example 2 is to use the multilayer diffraction optical element of materials A 2 and L2, and example 3 uses A3 and L3, and example 4 uses A4 and L4, and example 5 uses A6 and L6.Comparative example 1 is to use the multilayer diffraction optical element of materials A 5 and L5, and comparative example 2 uses A7 and L7, and comparative example 3 uses A8 and L8, and comparative example 4 uses L-BAL35 and L9.Shape (height and spacing width) at the diffraction grating of example shown in the table 4 1～5 and comparative example 1～4.
Configuration at the multilayer diffraction optical element of example shown in the table 5 6～11.Example 6 is to use the diffraction optical element of high-refractivity and low-dispersion materials A 3 and the multilayer diffraction optical element of the diffraction optical element that uses the high chromatic dispersion material T1 of low-refraction.Similarly, example 7 is to use the multilayer diffraction optical element of materials A 4 and T2, and example 8 uses A5 and T3, and example 9 uses A6 and T4, and example 10 uses A7 and T5, and example 11 uses A8 and T6.Shape (height and spacing width) at the diffraction grating of example shown in the table 5 6～11.
The assessment of diffraction efficiency
By prepare the refraction efficient of each multilayer diffraction optical element of sample measurement in following mode.
At first, similar with the manufacture method of the diffraction optical element that uses Fig. 5～7A and Fig. 7 B explanation, use the diffraction optical element of high-refractivity and low-dispersion material to be produced.But L-BAL 35 glass in the comparative example 4 (being made by OHARA INC.) are prepared as similar shape by cutting and polishing.
Then, be placed in sheet glass 13 on the formation anchor clamps 15 at the high-refractivity and low-dispersion material that forms on the sheet glass 13, then, the high chromatic dispersion material 16 of low-refraction is dropped in (Fig. 8 A) on the high-refractivity and low-dispersion material 7.On this material 16, place sheet glass 13, thus this material 16 is stretched and launch, make the thickness of resin become high 10 μ m of height (Fig. 8 B) than grating so that it is manufactured sample.This sample is at 20mW/cm
2With under 1000 seconds the condition by high pressure silver lamp (EXECURE 250, and by HOYA CANDEOOPTRONICS CO., LTD makes) irradiation, make sample solidifies thus.The sample that solidifies is removed, and measured in the diffraction efficiency of 25 ℃ and 60 ℃.
Diffraction efficiency is to use the resins identical with diffraction optical element with the light quantity irradiation of the design order of diffraction grating and having transmissivity under the situation of substrate upper member of identical thickness.The thickness identical with diffraction optical element means the average film thickness of diffraction optical element.Result at example shown in the table 4 1～5 and comparative example 1～4.Result at example shown in the table 5 6～11.
The measurement of solar flare coefficient
Measure the solar flare coefficient of each multilayer diffraction optical element in the following manner.The light of 15 degree of tilting are allowed to enter multilayer diffraction optical element 100, and, the back of the integrating sphere by taking off spectrophotometer (U4000, by Hitachi, Ltd. makes) and allow the diffraction light of design order pass, and the solar flare light beyond this light is measured.Result at example shown in the table 4 1～5 and comparative example 1～4.Result at example shown in the table 5 6～11.
Table 1
Table 2
| Fine inorganic particle | Organic principle | Optical characteristics | ||||
| Type | Content (v%) | Type | Content (v%) | Refractive index n d | Abbe number vd | |
| The high chromatic dispersion material L1 of low-refraction | ITO | 16.0 | Ultraviolet curing acryl resin C | 84.0 | 1.570 | 19.5 |
| The high chromatic dispersion material L2 of low-refraction | ITO | 14.1 | Ultraviolet curing acryl resin C | 85.9 | 1.565 | 20.8 |
| The high chromatic dispersion material L3 of low-refraction | ITO | 12.9 | Ultraviolet curing acryl resin C | 87.1 | 1.561 | 21.9 |
| The high chromatic dispersion material L4 of low-refraction | ITO | 7.9 | Ultraviolet curing acryl resin C | 92.1 | 1.546 | 27.6 |
| The high chromatic dispersion material L5 of low-refraction | ITO | 5.4 | Ultraviolet curing acryl resin C | 94.6 | 1.539 | 32.1 |
| The high chromatic dispersion material L6 of low-refraction | ITO | 7.6 | Ultraviolet curing acryl resin C | 92.4 | 1.546 | 28.0 |
| The high chromatic dispersion material L7 of low-refraction | ITO | 4.8 | Ultraviolet curing acryl resin C | 95.2 | 1.537 | 33.3 |
| The high chromatic dispersion material L8 of low-refraction | ITO | 2.8 | Ultraviolet curing acryl resin C | 97.2 | 1.531 | 38.9 |
| The high chromatic dispersion material L9 of low-refraction | ITO | 8.7 | Ultraviolet curing acryl resin C | 91.3 | 1.549 | 26.5 |
Table 3
| Fine inorganic particle | Organic principle | Optical characteristics | ||||
| Type | Content (v%) | Type | Content (v%) | Refractive index n d | Abbe number vd | |
| The high chromatic dispersion material T1 of low-refraction | ITO | 21.6 | Ultraviolet curing acryl resin D | 78.4 | 1.527 | 14.1 |
| The high chromatic dispersion material T2 of low-refraction | ITO | 17.3 | Ultraviolet curing acryl resin D | 82.7 | 1.508 | 16.1 |
| The high chromatic dispersion material T3 of low-refraction | ITO | 15.2 | Ultraviolet curing acryl resin D | 84.8 | 1.499 | 17.3 |
| The high chromatic dispersion material T4 of low-refraction | ITO | 16.8 | Ultraviolet curing acryl resin D | 83.2 | 1.506 | 16.4 |
| The high chromatic dispersion material T5 of low-refraction | ITO | 14.6 | Ultraviolet curing acryl resin D | 85.4 | 1.496 | 17.8 |
| The high chromatic dispersion material T6 of low-refraction | ITO | 13.0 | Ultraviolet curing acryl resin D | 87.0 | 1.489 | 19.0 |
Table 4
| The high-refractivity and low-dispersion material | The high chromatic dispersion material of low-refraction | Refractive index difference Δ nd | The diffraction grating shape | The minimum value of diffraction efficiency | The solar flare coefficient | |||||||
| Optical characteristics | Optical characteristics | Diffraction grating thickness μ m | Spacing width μ m | Room temperature (23 ℃) % | 60℃ ％ | ％ | ||||||
| Refractive index n d | Abbe number vd | Refractive index n d | Abbe number vd | |||||||||
| Example 1 | High-refractivity and low-dispersion materials A 1 | 1.621 | 44.1 | The high chromatic dispersion material L1 of low-refraction | 1.570 | 19.5 | 0.051 | 11.5 | 80 | 99.9 | 99.8 | 0.5 |
| Example 2 | High-refractivity and low-dispersion materials A 2 | 1.610 | 44.6 | The high chromatic dispersion material L2 of low-refraction | 1.565 | 20.8 | 0.045 | 13.0 | 80 | 99.9 | 99.8 | 0.6 |
| Example 3 | High-refractivity and low-dispersion materials A 3 | 1.602 | 45.0 | The high chromatic dispersion material L3 of low-refraction | 1.561 | 21.9 | 0.041 | 14.3 | 80 | 99.9 | 99.8 | 0.7 |
| Example 4 | High-refractivity and low-dispersion materials A 4 | 1.571 | 46.7 | The high chromatic dispersion material L4 of low-refraction | 1.546 | 27.6 | 0.024 | 23.9 | 80 | 99.8 | 99.7 | 1.7 |
| Example 5 | High-refractivity and low-dispersion materials A 6 | 1.576 | 56.4 | The high chromatic dispersion material L6 of low-refraction | 1.546 | 28.0 | 0.031 | 18.1 | 80 | 99.9 | 99.9 | 1.1 |
| Comparative example 1 | High-refractivity and low-dispersion materials A 5 | 1.556 | 47.2 | The high chromatic dispersion material L5 of low-refraction | 1.539 | 32.1 | 0.017 | 36.1 | 80 | 99.3 | 99.1 | 3.1 |
| Comparative example 2 | High-refractivity and low-dispersion materials A 7 | 1.558 | 54.7 | The high chromatic dispersion material L7 of low-refraction | 1.537 | 33.3 | 0.021 | 28.3 | 80 | 99.9 | 99.9 | 2.2 |
| Comparative example 3 | High-refractivity and low-dispersion materials A 8 | 1.543 | 53.3 | The high chromatic dispersion material L8 of low-refraction | 1.531 | 38.9 | 0.012 | 48.5 | 80 | 99.9 | 99.9 | 3.8 |
| Comparative example 4 | L-BAL35 (glass: make) by OHARA | 1.589 | 60.8 | The high chromatic dispersion material L9 of low-refraction | 1.549 | 26.5 | 0.040 | 14.6 | 80 | 99.8 | 75 | 0.8 |
Table 5
| The high-refractivity and low-dispersion material | The high chromatic dispersion material of low-refraction | Refractive index difference Δ nd | The diffraction grating shape | The minimum value of diffraction efficiency | The solar flare coefficient | |||||||
| Optical characteristics | Optical characteristics | Diffraction grating thickness μ m | Spacing width μ m | Room temperature (23 ℃) % | 60℃ ％ | ％ | ||||||
| Refractive index n d | Abbe number vd | Refractive index n d | Abbe number vd | |||||||||
| Example 6 | High-refractivity and low-dispersion materials A 3 | 1.602 | 45.0 | The high chromatic dispersion material L1 of low-refraction | 1.527 | 14.1 | 0.075 | 7.3 | 80 | 99.9 | 99.8 | 0.2 |
| Example 7 | High-refractivity and low-dispersion materials A 4 | 1.571 | 46.7 | The high chromatic dispersion material L2 of low-refraction | 1.508 | 16.1 | 0.062 | 9.0 | 80 | 99.9 | 99.7 | 0.3 |
| Example 8 | High-refractivity and low-dispersion materials A 5 | 1.556 | 47.2 | The high chromatic dispersion material L3 of low-refraction | 1.499 | 17.3 | 0.057 | 10.2 | 80 | 99.9 | 99.7 | 0.4 |
| Example 9 | High-refractivity and low-dispersion materials A 6 | 1.576 | 56.4 | The high chromatic dispersion material L4 of low-refraction | 1.506 | 16.4 | 0.070 | 8.1 | 80 | 99.9 | 99.5 | 0.2 |
| Example 10 | High-refractivity and low-dispersion materials A 7 | 1.558 | 54.7 | The high chromatic dispersion material L6 of low-refraction | 1.496 | 17.8 | 0.062 | 9.5 | 80 | 99.9 | 99.5 | 0.3 |
| Example 11 | High-refractivity and low-dispersion materials A 8 | 1.543 | 53.3 | The high chromatic dispersion material L5 of low-refraction | 1.489 | 19.0 | 0.054 | 10.8 | 80 | 99.9 | 99.3 | 0.4 |
Measure and assessment result
(example 1～5)
Can clearly be seen that the refractive index n of the high-refractivity and low-dispersion material in the example 1～5 from table 4
dFor more than or equal to 1.57 and smaller or equal to 1.63, and Abbe number v
dFor more than or equal to 44 and smaller or equal to 57.The refractive index n of the high chromatic dispersion material of low-refraction
dFor more than or equal to 1.54 and smaller or equal to 1.57, and Abbe number v
dFor more than or equal to 19 and smaller or equal to 28.Refractive index difference between the high chromatic dispersion material of high-refractivity and low-dispersion material and low-refraction is more than or equal to 0.024 and smaller or equal to 0.051.
Fig. 9～13rd, the diagrammatic sketch of the diffraction efficiency of each wavelength of the multilayer diffraction optical element in the expression example 1～5.Can clearly be seen that from table 4 and Fig. 9～13 for any situation of 23 ℃ and 60 ℃, the diffraction efficiency of example 1～5 is 99% or bigger, and is fabulous.As shown in table 4, the solar flare coefficient of example 1～5 is 1.7% or littler, and is fabulous.
(comparative example 1～3)
Can clearly be seen that the refractive index n of the high-refractivity and low-dispersion material in the comparative example 1～3 from table 4
dFor more than or equal to 1.54 and smaller or equal to 1.56, and Abbe number v
dFor more than or equal to 47 and smaller or equal to 55.The refractive index n of the high chromatic dispersion material of low-refraction
dFor more than or equal to 1.53 and smaller or equal to 1.54, and Abbe number v
dFor more than or equal to 32 and smaller or equal to 39.For any situation, the refractive index difference between the high chromatic dispersion material of high-refractivity and low-dispersion material and low-refraction is more than or equal to 0.011 and smaller or equal to 0.023.
Figure 14～16th, the diagrammatic sketch of the diffraction efficiency of each wavelength of the multilayer diffraction optical element in the expression comparative example 1～3.For any situation of 23 ℃ and 60 ℃, the diffraction efficiency of comparative example 1～3 is 99% or bigger, and is fabulous.But as shown in table 4, the solar flare coefficient of comparative example 1～3 is 2.2% or bigger, and to be difficult to this be good.
(comparative example 4)
Can clearly be seen that from table 4, in the comparative example 4 as the refractive index n of the L-BAL35 of high-refractivity and low-dispersion material
dBe 1.589, and Abbe number v
dBe 60.8.The refractive index n of the high chromatic dispersion material of low-refraction
dBe 1.549, and Abbe number v
dBe 26.5.Refractive index difference between the high chromatic dispersion material of high-refractivity and low-dispersion material and low-refraction is 0.040.
Linear expansion coefficient as the L-BAL35 of the high-refractivity and low-dispersion material in table 4 comparative example 4 is 7.0 * 10
-6/ ℃, and be minimum.Thus, the high chromatic dispersion L9 of the temperature dependency of refractive index and low-refraction is different greatly.Figure 17 is the diagrammatic sketch of diffraction efficiency of each wavelength of the multilayer diffraction optical element of expression in the comparative example 4.Though the diffraction efficiency at 26 ℃ of comparative examples 4 is 99% or bigger, is 75% and reduces to a great extent 60 ℃ of diffraction efficiencies.
(example 6～11)
Can clearly be seen that the refractive index n of the high-refractivity and low-dispersion material in the example 6～11 from table 5
dFor more than or equal to 1.54 and smaller or equal to 1.61, and Abbe number v
dFor more than or equal to 44 and smaller or equal to 57.The refractive index n of the high chromatic dispersion material of low-refraction
dFor more than or equal to 1.48 and smaller or equal to 1.53, and Abbe number v
dFor more than or equal to 14 and smaller or equal to 20.For any situation, the refractive index difference between the high chromatic dispersion material of high-refractivity and low-dispersion material and low-refraction is more than or equal to 0.053 and smaller or equal to 0.075.
Figure 18～23rd, the diagrammatic sketch of the diffraction efficiency in each wavelength of the multilayer diffraction optical element in the expression example 6～11.For arbitrary situation of 23 ℃ and 60 ℃, the diffraction efficiency of example 1～5 is 99% or bigger, and is fabulous.As shown in table 5, the solar flare coefficient of example 1～5 is 0.4% or littler, and is fabulous.
From these results, in with the situation that does not have the stacked high-refractivity and low-dispersion material that is dispersed with fine particle of at interval mode and the multilayer diffraction optical element of the high chromatic dispersion material of low-refraction that is dispersed with fine particle therebetween, the refractive index of the d line of high-refractivity and low-dispersion material is taken as more than or equal to 1.54 and smaller or equal to 1.63, and Abbe number is taken as more than or equal to 44 and smaller or equal to 57, the refractive index of the d line of the high chromatic dispersion material of low-refraction is taken as more than or equal to 1.48 and smaller or equal to 1.57, and Abbe number is taken as more than or equal to 14 and smaller or equal to 28, and the refractive index difference of the d line between the high chromatic dispersion material of high-refractivity and low-dispersion material and low-refraction is taken as more than or equal to 0.024 and smaller or equal to 0.075, make multilayer diffraction optical element to be implemented, wherein diffraction efficiency is 99% or bigger, the shape transferability is good, and because the fluctuation of the transmissivity that temperature variation causes is less.
That is, the optical element by the stacked organic resin that comprises therebetween not the high-refractivity and low-dispersion that is dispersed with fine inorganic particle at interval and the organic resin of the high chromatic dispersion of low-refraction that is dispersed with fine inorganic particle forms optical element of the present invention.As a result of, diffraction efficiency can increase, and since the distortion that causes of interfacial stress can be suppressed, and with since the change of the variation of the refractive index difference between the organic resin that difference between the absorption coerfficient and the difference between the linear expansion coefficient cause can reduce.
Though with reference to illustrative example the present invention has been described, has should be understood that to the invention is not restricted to disclosed illustrative example.The scope of the claim of enclosing should be endowed the wideest explanation to comprise all such changes and equivalent configurations and function.
Claims (8)
1. multilayer diffraction optical element comprises:
Transparency carrier (3);
At least on a face, have the diffraction grating shape and comprise the ground floor (1,2) of relative high-refractivity and low-dispersion material; With
At least on a face, have the diffraction grating shape and comprise the second layer (1,2) of the high chromatic dispersion material of relative low-refraction,
Wherein, the ground floor and the second layer are laminated on the transparency carrier, make each diffraction grating shape not have mode at interval therebetween mutually toward each other;
Ground floor comprises first organic resin (4a) that contains first fine inorganic particle (5a), and the second layer comprises second organic resin (4b) that contains second fine inorganic particle (5b) different with first fine inorganic particle; And
The refractive index of the d line of high-refractivity and low-dispersion material is more than or equal to 1.54 and smaller or equal to 1.63, and Abbe number is more than or equal to 44 and smaller or equal to 57, and, the refractive index of the d line of the high chromatic dispersion material of low-refraction is more than or equal to 1.48 and smaller or equal to 1.57, and Abbe number is more than or equal to 14 and smaller or equal to 28, and the refractive index difference of the d line between the high chromatic dispersion material of high-refractivity and low-dispersion material and low-refraction is more than or equal to 0.024 and smaller or equal to 0.075.
2. according to the multilayer diffraction optical element of claim 1, wherein, the average particle size of first fine inorganic particle and second fine inorganic particle is more than or equal to 1nm and smaller or equal to 100nm.
3. according to the multilayer diffraction optical element of claim 2, wherein, first fine inorganic particle comprises at least a type that is selected from Al, Zr, Y, Ga, La and oxide thereof and compound, and has more than or equal to 1.70 and smaller or equal to the refractive index of its d line of 2.5 with more than or equal to 30 and smaller or equal to 90 Abbe number.
4. according to the multilayer diffraction optical element of claim 2, wherein, the volume content of first fine inorganic particle in the ground floor is 1～29vol%.
5. according to the multilayer diffraction optical element of claim 1, wherein, second fine inorganic particle is the electrically conducting transparent material.
6. according to the multilayer diffraction optical element of claim 5, wherein, the electrically conducting transparent material is ITO.
7. according to the multilayer diffraction optical element of claim 1, wherein, the organic resin that comprises in ground floor comprises at least a type that is selected from acryl resin, vinyl and epoxy resin, and the organic resin that comprises in the second layer comprises at least a type that is selected from acrylic based resin, fluorinated acrylamide acidic group resin, silicone and fluororesin.
8. according to the multilayer diffraction optical element of claim 7, wherein, the organic resin that comprises in the ground floor and the second layer comprises ultraviolet curable resin.
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| JP5424623B2 (en) * | 2008-01-21 | 2014-02-26 | キヤノン株式会社 | Resin composition and optical element, diffractive optical element and laminated diffractive optical element molded thereby |
| JP5590851B2 (en) * | 2008-12-10 | 2014-09-17 | キヤノン株式会社 | Diffractive optical element, laminated diffractive optical element and method of manufacturing the same |
| WO2010140341A1 (en) * | 2009-06-03 | 2010-12-09 | パナソニック株式会社 | Diffractive optical element |
| JP2011022255A (en) | 2009-07-14 | 2011-02-03 | Canon Inc | Diffraction optical element and optical system having the same |
| JP5479022B2 (en) * | 2009-10-19 | 2014-04-23 | キヤノン株式会社 | Optical material and multilayer diffractive optical element |
| JP5059079B2 (en) * | 2009-10-21 | 2012-10-24 | キヤノン株式会社 | Laminated diffractive optical element and optical system |
| JP2011154362A (en) | 2009-12-28 | 2011-08-11 | Panasonic Corp | Diffractive optical element and optical device |
| CN101813797B (en) * | 2010-03-03 | 2012-02-22 | 长春理工大学 | Optimal design method of multilayer diffraction optical element |
| JP2011257617A (en) * | 2010-06-10 | 2011-12-22 | Canon Inc | Diffraction optical element and optical system having the same |
| JP5615065B2 (en) * | 2010-07-07 | 2014-10-29 | キヤノン株式会社 | Diffractive optical element, optical system and optical instrument |
| JP5854593B2 (en) * | 2010-11-17 | 2016-02-09 | キヤノン株式会社 | Multilayer diffractive optical element |
| JP5773668B2 (en) * | 2011-02-03 | 2015-09-02 | キヤノン株式会社 | Multilayer diffractive optical element |
| JP5863265B2 (en) * | 2011-04-08 | 2016-02-16 | キヤノン株式会社 | Optical element and multilayer diffractive optical element |
| JP5271457B1 (en) * | 2011-08-24 | 2013-08-21 | パナソニック株式会社 | Diffractive optical element and method of manufacturing diffractive optical element |
| US9835765B2 (en) | 2011-09-27 | 2017-12-05 | Canon Kabushiki Kaisha | Optical element and method for manufacturing the same |
| JPWO2014129206A1 (en) * | 2013-02-25 | 2017-02-02 | パナソニックＩｐマネジメント株式会社 | Optical element, composite optical element, interchangeable lens, and imaging device |
| JP6282257B2 (en) * | 2015-12-10 | 2018-02-21 | キヤノン株式会社 | Laminated diffractive optical element and optical system |
| JP6887761B2 (en) | 2016-05-31 | 2021-06-16 | キヤノン株式会社 | Manufacturing method of laminated diffractive optical element |
| EP3572396A4 (en) | 2017-01-17 | 2020-11-18 | Nikon Corporation | (meth)acrylate compound, additive for optical resin, optical element, and optical device |
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| DE102019100794A1 (en) * | 2018-12-20 | 2020-06-25 | Osram Opto Semiconductors Gmbh | LASER DEVICE AND METHOD FOR PRODUCING A LASER DEVICE |
| JP7414399B2 (en) | 2019-04-01 | 2024-01-16 | キヤノン株式会社 | Diffractive optical elements, optical instruments, imaging devices, and methods for manufacturing diffractive optical elements |
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| ATE467849T1 (en) | 2010-05-15 |
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